WO2013146718A1 - Bande adhésive pour prévenir le bioencrassement aquatique - Google Patents

Bande adhésive pour prévenir le bioencrassement aquatique Download PDF

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Publication number
WO2013146718A1
WO2013146718A1 PCT/JP2013/058654 JP2013058654W WO2013146718A1 WO 2013146718 A1 WO2013146718 A1 WO 2013146718A1 JP 2013058654 W JP2013058654 W JP 2013058654W WO 2013146718 A1 WO2013146718 A1 WO 2013146718A1
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Prior art keywords
layer
antifouling
adhesive tape
base material
aquatic organism
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PCT/JP2013/058654
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English (en)
Japanese (ja)
Inventor
倉田　直記
内藤　友也
太樹 末吉
鈴木　聡
原　和孝
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to EP13768575.6A priority Critical patent/EP2832808A4/fr
Priority to US14/388,499 priority patent/US20150079345A1/en
Publication of WO2013146718A1 publication Critical patent/WO2013146718A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2605/12—Ships
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
    • B63B59/04—Preventing hull fouling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/006—Presence of polysiloxane in the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the present invention relates to an aquatic organism adhesion preventing adhesive tape.
  • the present invention is that underwater organisms adhere to underwater structures (such as ships, buoys, harbor facilities, offshore oilfield facilities, waterways for power plant cooling water, waterways for factory cooling water, water floating passages, etc.).
  • the present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.
  • antifouling paint In order to prevent such damage, antifouling paint has been conventionally applied to underwater structures. Antifouling paints have long contained toxic antifouling agents such as organotin compounds and now cuprous oxide. The adhesion growth of marine organisms can be almost suppressed by the toxicity of antifouling paints, but toxic antifouling agents such as organotin compounds and cuprous oxide have a considerable adverse effect on the human body and the environment. It becomes. Further, when the antifouling paint is dried after being applied, about 30% by weight of the organic solvent (VOC) is volatilized, which adversely affects the work environment and the surrounding environment. In spray coating, in addition to discharging VOC into the atmosphere, it is said that 10% to 20% by weight of the paint is scattered around by the wind.
  • VOC organic solvent
  • antifouling paints so far have an adhesion inhibiting effect on marine organisms, they have a great adverse effect on the human body and the environment, and the current situation is that many problems have not been solved. .
  • an antifouling tape composed of two layers of silicone rubber and an adhesive
  • the silicone rubber layer responsible for the antifouling effect does not contain an antifouling agent such as oil, and is a silicone rubber itself.
  • the antifouling agent is not included, the adhesion of marine organisms can be suppressed by its water repellency in the short term, but the antifouling effect cannot be sustained in the long term.
  • an antifouling tape is composed of two layers of silicone rubber and an adhesive, there is a great concern about strength.
  • silicone rubber has a very low strength at break, and therefore, when such an antifouling tape is peeled off after use, it is difficult to peel off as a tape state, which is not practical.
  • Patent Document 4 a sheet-like tape has been proposed in which a silicone elastomer is provided on a base material via a primer and an adhesive layer is provided on the opposite side of the base material (see Patent Document 4).
  • Patent Document 4 since there is no description regarding the adhesive composition that can be used in water and no description regarding adhesive strength, Patent Document 4 is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape.
  • Patent Document 4 does not have such description at all, and is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape.
  • the problem of the present invention is that it can exhibit good adhesion even in water, has good mechanical properties, is easy to peel off, has a small surface roughness, can maintain an antifouling effect over a long period of time, less environmental load, the weight is light, can maintain a stable quality, adhesion of aquatic organisms can be effectively prevented, when attached to the hull may contribute to CO 2 emissions reduction and fuel economy improvement, aquatic organisms It is providing the adhesion prevention adhesive tape.
  • the aquatic organism adhesion preventing adhesive tape of the present invention is An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order,
  • the antifouling layer has a 10-point average surface roughness Rz of 5.0 ⁇ m or less.
  • the arithmetic average surface roughness Ra of the antifouling layer is 1.0 ⁇ m or less.
  • the antifouling layer contains a silicone resin.
  • the antifouling layer contains an antifouling agent.
  • the content ratio of the antifouling agent to the silicone resin is 2% by weight or more.
  • the antifouling agent is at least one selected from silicone oil, liquid paraffin, and surfactant.
  • the base material layer has an elongation of 100% or more and a stress at break of 10 MPa or more.
  • the adhesive layer has a 180-degree peel adhesive strength of 30 N / 20 mm or less at 23 ° C. and a tensile speed of 300 mm / min.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer in contact with seawater is 1.1 times the compression elastic modulus of the pressure-sensitive adhesive layer before seawater contact. That's it.
  • good adhesiveness can be expressed even in water, it has good mechanical properties, is easy to peel off, has a small surface roughness, can maintain an antifouling effect over a long period of time, less environmental load, the weight is light, can maintain a stable quality, adhesion of aquatic organisms can be effectively prevented, when attached to the hull may contribute to CO 2 emissions reduction and fuel economy improvement, aquatic organisms
  • An adhesion-preventing adhesive tape can be provided.
  • the aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer and an adhesive layer in this order.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has any appropriate other layer as long as the antifouling layer, the base material layer, and the pressure-sensitive adhesive layer are included in this order, as long as the effects of the present invention are not impaired. May be.
  • the thickness of the aquatic organism adhesion prevention adhesive tape of this invention is set to arbitrary appropriate thickness in the range which does not impair the effect of this invention by the thickness of each layer contained in it.
  • the thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 50 ⁇ m to 5000 ⁇ m.
  • FIG. 1 shows a schematic cross-sectional view of an example of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the aquatic organism adhesion prevention adhesive tape 100 of this invention contains the antifouling layer 2, the base material layer 3, and the adhesion layer 4 in this order.
  • a release film 1 may be provided on the surface of the antifouling layer 2 or the surface of the adhesive layer 4.
  • the antifouling layer has a ten-point average surface roughness Rz of 5.0 ⁇ m or less.
  • the 10-point average surface roughness Rz of the antifouling layer is preferably 4.5 ⁇ m or less, more preferably 4.0 ⁇ m or less, still more preferably 3.0 ⁇ m or less, and particularly preferably 2.5 ⁇ m or less. Yes, most preferably 2.0 ⁇ m or less.
  • the lower limit value of the ten-point average surface roughness Rz of the antifouling layer is preferably as small as possible, but is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, considering the materials and the like. Preferably it is 0.1 micrometer or more.
  • the aquatic organism adhesion preventing adhesive tape of the present invention can effectively prevent the aquatic organism from adhering. It can contribute to fuel efficiency improvement and emission CO 2 reduction. A method for measuring the ten-point average surface roughness Rz will be described later.
  • the antifouling layer has an arithmetic average surface roughness Ra of preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, still more preferably 0.6 ⁇ m or less, and particularly preferably 0.4 ⁇ m or less. And most preferably 0.2 ⁇ m or less.
  • the lower limit of the arithmetic average surface roughness Ra of the antifouling layer is preferably as small as possible, but is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, considering materials and the like.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can more effectively prevent aquatic organisms from adhering, and is attached to the hull. It may contribute further by CO 2 emissions reduction and fuel economy improvement. A method for measuring the arithmetic average surface roughness Ra will be described later.
  • means for keeping the ten-point average surface roughness Rz of the antifouling layer within the above range preferably means for putting the arithmetic average surface roughness Ra of the antifouling layer within the above range.
  • an appropriate selection of the composition of the antifouling layer and an appropriate selection of a method for forming the antifouling layer can be mentioned.
  • the antifouling layer preferably contains a silicone resin.
  • the content ratio of the silicone resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, still more preferably 45% by weight to 96% by weight, Particularly preferred is 50 to 95% by weight.
  • the content ratio of the silicone resin in the antifouling layer is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the mechanical characteristics of the antifouling layer can be sufficiently expressed.
  • the content ratio of the silicone resin in the antifouling layer is less than 30% by weight, the mechanical properties of the antifouling layer may be deteriorated.
  • the content ratio of the silicone resin in the antifouling layer exceeds 98% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.
  • any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent. In the present invention, among these, a one-component room temperature curable (RTV) resin and a two-component room temperature curable (RTV) resin are preferable.
  • RTV room temperature curable
  • RTV room temperature curable
  • Examples of the one-component RTV resin include KE-3475, KE-45S, KE-445, KE-44, KE-441, KE-3497, and KE-4896 manufactured by Shin-Etsu Chemical Co., Ltd. .
  • Examples of the two-component RTV resin include KE-106, KE-66, KE-1031, and KE-1800 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the silicone resin can be easily peeled off due to elastic deformation of the resin surface due to water pressure at the time of water washing removal.
  • a silicone resin having such physical properties is preferred.
  • Such a silicone resin has a 100% modulus (tensile stress) of the silicone resin of preferably 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 6 MPa.
  • Such silicone resin is preferably soluble in an organic solvent.
  • the antifouling layer preferably contains an antifouling agent. Only one type of antifouling agent may be used, or two or more types may be used.
  • the antifouling agent migrates to the surface of the silicone resin as a matrix and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. Furthermore, since it is non-hydrolyzable, it can exhibit the effect of maintaining a high antifouling effect for a long period of time.
  • the content ratio of the antifouling agent to the silicone resin is preferably 2% by weight or more, more preferably 2% by weight to 200% by weight, and further preferably 3% by weight to 150% by weight. Particularly preferred is 4 to 120% by weight, and most preferred is 5 to 100% by weight.
  • the content ratio of the antifouling agent to the silicone resin is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the appearance characteristics and mechanical characteristics of the antifouling layer can be sufficiently expressed.
  • the content ratio of the antifouling agent to the silicone resin is less than 2% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.
  • the content of the antifouling agent relative to the silicone resin exceeds 200% by weight, the appearance of the final molded product or the film may be deteriorated, and the antifouling layer strength is lowered and the antifouling property cannot be maintained. There is a fear.
  • any appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired.
  • examples of such an antifouling agent include silicone oil, liquid paraffin, surfactant, wax, petrolatum, animal fats, fatty acids and the like.
  • the antifouling agent is preferably at least one selected from silicone oil, liquid paraffin, and surfactant.
  • the silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation.
  • any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired.
  • Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.
  • R 1 is the same or different and represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a fluoroalkyl group, a polyether group, or a hydroxyl group
  • R 2 is the same or Differently, it represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a polyether group or a fluoroalkyl group
  • n represents an integer of 0 to 150.
  • R 1 in the general formula (I) is preferably a methyl group, a phenyl group, or a hydroxyl group.
  • R 2 in the general formula (I) is preferably a methyl group, a phenyl group, or a 4-trifluorobutyl group.
  • the number average molecular weight of the silicone oil represented by the general formula (I) is preferably 180 to 20000, and more preferably 1000 to 10,000.
  • the viscosity of the silicone oil represented by the general formula (I) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.
  • silicone oil represented by the general formula (I) specifically, for example, terminal hydroxyl group-containing dimethyl silicone oil R 1 at both ends or one end is a hydroxyl group, all of R 1 and R 2 is a methyl group And dimethyl silicone oils in which some of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups.
  • silicone oils represented by the general formula (I) include KF96L, KF96, KF69, KF99, KF50, KF54, KF410, KF412, KF414, FL, Toray Dow Corning manufactured by Shin-Etsu Chemical Co., Ltd. BY16-846, SF8416, SH200, SH203, SH230, SF8419, FS1265, SH510, SH550, SH710, FZ-2110, and FZ-2203 manufactured by Corporation may be mentioned.
  • surfactant examples include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
  • antifouling agents diatomaceous adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinol), and biological repellents may be used.
  • pharmaceuticals such as medetomidine
  • enzyme activity inhibitors such as alkylphenols and alkylresorcinol
  • biological repellents may be used.
  • the antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired.
  • the thickness of the antifouling layer may be any appropriate thickness depending on the application or use environment of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the thickness of the antifouling layer is preferably 5 ⁇ m to 500 ⁇ m. When the thickness of the antifouling layer is within the above range, the antifouling effect is effective for a sufficiently long time, and the handling property is excellent. When the thickness of the antifouling layer is less than 5 ⁇ m, the period during which the antifouling effect is effective is shortened and may not be practical. If the antifouling layer is thicker than 500 ⁇ m, the aquatic organism adhesion-preventing adhesive tape of the present invention becomes thick and increases in weight, resulting in poor handling, large irregularities at the joints of the tape, and dirt. There is a fear.
  • any appropriate base material layer can be adopted as long as the effects of the present invention are not impaired.
  • a material for the base material layer is preferably excellent in water resistance, strength, flexibility and tearability.
  • the material for the base material layer include polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) ) And the like.
  • the material of such a base material layer may be only one type or two or more types.
  • the elongation of the base material layer is preferably 100% or more, more preferably 120% or more, and further preferably 150% or more.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can follow the shape of various adherends well and can be affixed to a flat surface well. It can be satisfactorily applied to curved surface portions, 90-degree angle portions, acute angle portions, and the like.
  • the elongation of the base material layer is less than 100%, the shape of various adherends cannot be sufficiently followed, and wrinkles and unbonded portions of the adhesive may be generated, which may cause poor appearance and poor adhesion.
  • the upper limit of the elongation of the base material layer is preferably 2000% or less from the viewpoint of the strength of the base material layer.
  • the base material layer has a breaking stress of preferably 10 MPa or more, more preferably 12 MPa or more, and further preferably 15 MPa or more.
  • the stress at break of the base material layer is within the above range, the base material layer can be prevented from being cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend.
  • the stress at break of the base material layer is less than 10 MPa, the base material layer is frequently cut when the used aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention is peeled off from the adherend, and the working efficiency is extremely poor. There is a risk.
  • the upper limit of the breaking point stress of the base material layer is preferably 200 MPa or less from the viewpoint of the handleability of the base material layer.
  • the elastic modulus of the base material layer is preferably 4000 MPa or less, more preferably 1000 MPa or less, still more preferably 100 MPa or less, and particularly preferably 50 MPa or less.
  • the lower limit of the elastic modulus of the base material layer is preferably 0.1 MPa or more from the viewpoint of handleability of the base material layer.
  • the base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired.
  • additives include olefin resins, silicone polymers, liquid acrylic copolymers, tackifiers, anti-aging agents, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Polyethyleneimine, fatty acid amide, fatty acid ester, phosphate ester, lubricant, surfactant, filler and pigment (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, carbon black, etc.).
  • the base material layer preferably contains an ultraviolet absorber.
  • the weather resistance of the aquatic organism adhesion prevention adhesive tape of this invention improves because a base material layer contains a ultraviolet absorber.
  • the base material layer does not contain an ultraviolet absorber, the base material is likely to be deteriorated by sunlight during outdoor use, and it may be difficult to maintain the initial base material strength.
  • the base material layer is frequently cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend, and the work efficiency may be significantly deteriorated. There is.
  • the thickness of the base material layer is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 800 ⁇ m, and still more preferably 20 ⁇ m to 500 ⁇ m.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can be easily attached to a portion other than a flat surface such as a curved surface or an acute angle surface with good workability. Appearance defects such as wrinkles and floats are unlikely to occur on the surface.
  • the thickness of the base material layer is too thin, the handling property is deteriorated, the role as a base material cannot be played, and there is a possibility that it is not practical.
  • the thickness of the base material layer is too thick, it is impossible to sufficiently follow the shape of the adherend, the unevenness of the joint portion of the tape becomes large, and there is a possibility that it is easily stained.
  • a primer may be applied to the base material layer in advance, or a silane coupling agent may be added in advance.
  • adhesion to the base material layer may be low due to the low surface energy that is a characteristic of the silicone resin. If the adhesion between the antifouling layer and the base material layer is low, the antifouling layer that exhibits the antifouling effect peels off from the base material layer due to impact or physical damage during use, and the original antifouling effect continues. It may not be possible.
  • a primer is applied to the surface of the base material layer in advance to improve the adhesion to the antifouling layer, or silanol groups and alkoxysilane groups that react with the silicone resin are introduced into the base material layer with a silane coupling agent.
  • the adhesion can be improved by performing a condensation reaction with a reactive group on the base material layer during application of the condensation type silicone resin.
  • silane coupling agent Only one type of silane coupling agent may be used, or two or more types may be used. Specific examples of commercially available silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content ratio of the silane coupling agent in the base material layer is preferably 0.01% by weight to 10% by weight.
  • the content ratio of the silane coupling agent in the base material layer is preferably 0.01% by weight to 10% by weight.
  • any appropriate adhesive layer can be adopted as long as the effects of the present invention are not impaired.
  • the material for such an adhesive layer include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, and curable acrylic resin adhesives. Agents, silicone resin adhesives, and the like.
  • the material of the adhesive layer may be only one type or two or more types.
  • the adhesive layer has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably 30 N / 20 mm or less, more preferably 20 N / 20 mm or less, and further preferably 15 N / 20 mm or less.
  • the 180 degree peel adhesive force at 23 ° C. and a tensile speed of 300 mm / min is within the above range, the aquatic organism adhesion preventing adhesive tape of the present invention can be easily peeled off from the adherend. If the adhesive layer has a 180 degree peel adhesive force of 30 N / 20 mm at 23 ° C.
  • the lower limit of the 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min is preferably 5 N / 20 mm or more from the viewpoint of maintaining sufficient adhesive strength.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer in contact with seawater is preferably 1.1 times the compression elastic modulus of the pressure-sensitive adhesive layer before seawater contact. More preferably, it is 1.2 times or more, and more preferably 1.5 times or more.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer in contact with seawater is 1.1 times the compression elastic modulus of the pressure-sensitive adhesive layer before seawater contact, Can exhibit good adhesiveness.
  • the upper limit of the compression elastic modulus of the portion of the pressure-sensitive adhesive layer that is in contact with seawater with respect to the compression elastic modulus in the pressure-sensitive adhesive layer before seawater contact is from the viewpoint of handling properties. Preferably it is 100 times or less.
  • the thickness of the adhesive layer any appropriate thickness can be adopted depending on the application and use environment of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the thickness of the adhesive layer is preferably 10 ⁇ m or more.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 100 ⁇ m or less from the viewpoint of handleability.
  • the aquatic organism adhesion preventing adhesive tape of the present invention can be produced by any appropriate method.
  • a method of forming an antifouling layer by applying an antifouling layer forming material on the base material layer after pasting a separately prepared base material layer and an adhesive layer, and one of the base material layers.
  • a method of forming an adhesive layer by applying an adhesive layer forming material on the surface and forming an antifouling layer by applying an antifouling layer forming material to the other surface of the base material layer, the base layer forming material and the adhesive layer For example, a method of forming the antifouling layer by applying the antifouling layer forming material on the base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.
  • Examples of the method for applying the antifouling layer forming material on the base material layer include spraying, brushing, roller, curtain flow, roll, dip, and coater.
  • the antifouling layer-forming material is applied onto the base material layer by these methods, and the antifouling layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably from room temperature to 180 ° C.). can do.
  • a precision coater such as a comma coater is used to apply the antifouling layer forming material onto the base material layer.
  • Measurement condition Measurement method: VSI (vertical scanning interferometry method, Vertical Scan Interferometry method) Magnification of body lens: x2.5 FOV lens (internal lens) magnification: x 0.55 Measurement area: 20mm x 20mm A sample was placed on a measurement stage, and the surface roughness in the horizontal direction (X direction) and vertical direction (Y direction) was measured at a pitch of 10 ⁇ m under the above measurement conditions, and the average value was obtained. Measurement principle: The contrast peak value of interference fringes generated by the light reflected from the reference mirror inside the apparatus and the light reflected from the sample was converted into height, and the surface roughness was measured.
  • the ten-point average surface roughness Rz is the highest measured from the roughness curve in the direction of the average line, only the reference length L (here, 20 mm), and measured in the direction of the vertical magnification from the average line of the extracted portion.
  • Arithmetic average surface roughness Ra means that only a reference length L (20 mm in this case) is extracted from the roughness curve in the direction of the average line, and the X axis is in the direction of the average magnification of the extracted portion in the direction of the vertical magnification
  • y f (x)
  • the pressure-sensitive adhesive in the pressure-sensitive adhesive layer was transferred to a polyester film (trade name “S-10”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m) using a hand roller to obtain a pressure-sensitive adhesive sheet with a substrate. This was cut into a test piece size of 80 mm ⁇ 20 mm.
  • a plastic FRP plate reinforced by putting a glass cloth in an epoxy resin of 30 mm ⁇ 100 mm ⁇ thickness 2 mm was used.
  • the test piece was adhered to the adherend by reciprocating once with a 2 kg roller, and allowed to stand at 23 ° C. for 30 minutes, and then the initial 180-degree peel adhesive strength was measured.
  • the tensile speed was 300 mm / min.
  • ⁇ There is almost no attached organism, or even if it is attached, it is easily peeled off with a finger.
  • delta The state to which the adhesion organism has adhered to about 10% of the surface.
  • X A state in which attached organisms are attached to about 20% of the surface.
  • XX A state in which attached organisms are attached to about 30% or more of the surface.
  • a syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a base material syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is bonded to the base material syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illumination: 3). 4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and a substrate layer having a thickness of 150 ⁇ m was obtained.
  • the elongation was 420% and the stress at break was 27 MPa.
  • the acrylic monomer mixture was obtained by converting a part of the monomer into a polymer by adjusting the viscosity so that it can be applied by UV irradiation from above in a nitrogen stream.
  • To this acrylic monomer mixture 0.08 part by weight of 1,6-hexanediol diacrylate (HDDA) as a crosslinking agent was added, and the surface of the separator (trade name “MRF50”, manufactured by Mitsubishi Plastics, Inc., thickness 50 ⁇ m).
  • HDDA 1,6-hexanediol diacrylate
  • cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness: 38 ⁇ m) with a hand roller, and further irradiating with an ultraviolet lamp (BL type) (ultraviolet rays) Illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and an adhesive layer having a thickness of 50 ⁇ m was obtained. It was 13.3N / 20mm as a result of measuring the 180 degree
  • Example 1 ⁇ Preparation of antifouling layer forming material>
  • silicone oil SH200-100cs, non-reactive silicone oil, Shin-Etsu Chemical
  • KE-44 room temperature curable (RTV) resin, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the mixture was stirred using a homomixer, and the antifouling agent was uniformly dissolved or dispersed in the resin. After stirring, defoaming was performed to obtain an antifouling layer-forming material (1) for coating on the base material layer.
  • Example 6 In the formulation shown in Table 1, a silicone resin (KE-44, room temperature curable (RTV) resin, manufactured by Shin-Etsu Chemical Co., Ltd.) and a surfactant (DKS-NL-DASH400, non-ionic ether type interface) as an antifouling agent
  • an activator Diichi Kogyo Seiyaku Co., Ltd.
  • the mixture was stirred using a homomixer to uniformly dissolve or disperse the antifouling agent in the resin.
  • defoaming was performed to obtain an antifouling layer-forming material (5) for coating on a substrate.
  • an adhesive tape (5) was prepared in the same manner as in Example 1.
  • the evaluation results are shown in Table 2.
  • the aquatic organism adhesion preventing adhesive tape of the present invention can prevent aquatic organisms from adhering and breeding, underwater structures (ships, buoys, port facilities, offshore oilfield facilities, waterways for power plant cooling water, factory cooling) It can be suitably used for water channels and floating passages.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne une bande adhésive pour prévenir le bioencrassement aquatique, ladite bande adhésive étant douée d'une bonne performance d'adhérence même dans l'eau, a de bonnes caractéristiques mécaniques, est facile à décoller, présente une petite rugosité de surface, et peut exercer un effet anti-encrassement durable pendant longtemps. La bande adhésive selon l'invention a peu d'impact sur le corps humain et l'environnement ; elle est de poids léger, capable de conserver des qualités stables, et a la capacité de prévenir efficacement le bioencrassement aquatique. Quand elle est appliquée à la coque d'un bateau, la bande adhésive selon l'invention contribue à améliorer le rendement du carburant et à réduire les émissions de CO2. La bande adhésive pour prévenir le bioencrassement aquatique selon la présente invention comprend une couche anti-encrassement, une couche de substrat et une couche adhésive, dans cet ordre, et présente une rugosité de surface (Rz) moyenne sur dix points de 5,0 µm ou moins.
PCT/JP2013/058654 2012-03-29 2013-03-26 Bande adhésive pour prévenir le bioencrassement aquatique WO2013146718A1 (fr)

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US14/388,499 US20150079345A1 (en) 2012-03-29 2013-03-26 Adhesive tape for preventing aquatic biofouling

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JP2013203925A (ja) 2013-10-07
US20150079345A1 (en) 2015-03-19
EP2832808A1 (fr) 2015-02-04

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